Olefin disproportionation

ABSTRACT

A NOVEL CATALYST IS MANUFACTURED BY THE REACTION OF A METALLIC COMPOSITION HAVING THE FORMULA R(M(CO)5X) WHEREIN R IS SELECTED FROM THE GROUP CONSISTING OF ALKALI METAL IONS AND CATIONS OF THE TYPE J4Q WHEREIN Q IS SELECTED FROM THE GROUP CONSISTING OF NITROGEN, PHOSPHOROUS AND ARSENIC, AND J IS SELECTED FROM THE GROUP CONSISTING OF HYDROGEN AND C1-C30 HYDROCABYL RADICALS, M IS A GROUP VI-B METAL AND X IS A UNINEGATIVELY CHARGED LIGAND, SELECTED FROM THE GROUP CONSISTING OF HALIDE, CYANIDE, CYANATE, THIOCYANATE, AZIDE, ACETATE, TRIFLUOROACETATE AND STEARATE, WITH AN ACTIVATOR, SAID ACTIVATOR CONSISTING ESSENTIALLY OF AN ORGANOMETALLIC COMPOUND, SAID ORGANOMETALLIC COMPOUND SELECTED FROM THE GROUP CONSISTING OF COMPOUNDS HAVING THE GENERAL FORMULA RNLYM WHEREIN R IS INDEPENDENTLY SELECTED FROM THE GROUP CONSISTING OF C1 TO C30 HYDROCARBYL RADICALS, L IS SELECTED FROM THE GROUP CONSISTING OF GROUP I-A, II-A AND III-A METALS, AND METALS HAVING AN ATOMIC NUMBER OF FROM 3 TO 31, Y IS A HALIDE, N IS AN INTERGER OF FROM 1 TO 3, AND M IS AN INTEGER OF FROM 0 TO 3, N AND M HAVING TOTAL EQUAL TO THE VALENCE OF L, AT A TEMPEATURE OF FROM ABOUT-100 TO +150*C. AND A PRESSURE OF BETWEEN 0.1 AND 1,000 ATMOSPHERES, THE MOLAR RATIO OF ORGANOMETALLIC COMPOUND TO METALLIC COMPOSITION VARYING BETWEEN 0.5:1 AND 50:1, WHEREBY A CATALYST IS FORMED.

United States Patent 3,686,136 OLEFIN DISPROPORTIONATION Gerald Doyle,Somerville, N.J., assignor to Essu Research and Engineering Co. NoDrawing. Filed Oct. 1, 1969, Ser. No. 862,970 Int. Cl. C07c 3/62 US. Cl.252-429 B 18 Claims ABSTRACT OF THE DISCLOSURE A novel catalyst ismanufactured by the reaction of -a metallic composition having theformula R[M(CO) X] wherein R is selected from the group consisting ofalkali metal ions and cations of the type I Q wherein Q is selected fromthe group consisting of nitrogen, phosphorous and arsenic, and J isselected from the group consisting of hydrogen and C C- hydrocarbylradicals, M is a Group VI-B metal and X is a uninegatively chargedligand, selected from the group consisting of halide, cyanide, cyanate,thiocyanate, azide, acetate, trifluoroacetate and stearate, with anactivator, said activator consisting essentially of an organometalliccompound, said organometallic compound selected from the groupconsisting of compounds having the general formula r I Y wherein r isindependently selected from the group consisting of C t0 C hydrocarbylradicals, L is selected from the group consisting of Group I-A, H-A andIII-A metals, said metals having an atomic number of from 3 to 31, Y isa halide, n is an integer of from 1 to 3, and m is an integer of from Oto 3, n and m having a total equal to the valence of L, at a temperatureof from about 100 to +150 C. and a pressure of between 0.1 and 1,000atmospheres, the molar ratio of organometallic compound to metalliccomposition varying between 0.5:1 and 50:1, whereby a catalyst isformed.

BACKGROUND OF THE INVENTION This invention relates to a novel processfor producing a unique ionic catalyst, said catalyst being especiallyeifective for the disproportionation of olefins.

The disproportionation of olefins refers to those reactions in which oneor more olefinic compounds are transformed into other olefins ofdifferent molecular weights. The reaction can be regarded as consistingof the breaking of the double bonds of the reacting olefins and therecombination of the resulting fragments in such a manner that newolefinic products will result.

In the past a variety of catalysts had been known for this purpose.Typical of such catalysts is a catalyst comprising a VI-B metal complexrepresented by the formula [(L) M 2 wherein each (L) is a CO, R Q, 'RQO, P Q-QR or R (COO) ligand, each Z is a halogen or CN, SCN, OCN, orSnCl radical; M is Mo, W, M00, M00 W0, W0 preferably M0 or W; Q isphosphorous, arsenic, or antimony; a is 16, b is 1-2, generally 1 c is0-5, and the number of (L) and Z groups present in the complex is notgreater than the number required for the metal to achieve the closedshell electronic configuration of the next higher atomic number inertgas; x is a numher, generally 1, representing the polymeric state of thecomplex; R is an aromatic or saturated aliphatic hydrocarbon radical,including alkoxy and halo derivatives thereof, having up to 20 carbonatoms; m is 1 or 2; R is an aromatic, saturated aliphatic, orethylenically unsaturated hydrocarbon radical having up to 30 carbonatoms, R being monovalent when m is 1 and divalent when m is 2; with anorganometallic reducing agent.

Variations on the above catalyst are also known in which Group VIImetals are utilized as Well as Group V-III metals. Although thesecatalysts have proven to be somewhat successful in thedisproportionation of olefins their acceptance has been hinderedsomewhat by the great expense associated with their production. Inaddition, many of these catalysts have not shown great activityparticularly at lower temperatures, i.e. tempeartures in the range of 25to 40 C.

Heterogeneous catalysts which have been utilized for olefindisproportionation in the past have had only limited success asindicated by their relatively low activities and selectivities and therequirement that the reactions must be carried out in the vapor state.

SUMMARY OF THE INVENTION According to this invention it has unexpectedlybeen found that catalysts having the general formula when reacted withan organometallic compound of a Group I to III metal, preferably a LA,II-A, or III-A metal halide produce an extremely effective catalyst,especially for olefin disproportionation.

In the above formula R is a suitable cation chosen from any of severalunipositive cations, usually a tetraalkyl or aryl substituted Group Velement. M is a Group VI-B metal and X is a uninegatively charged ligandsuch as a halide or a pseudohalide.

The contacting between the Group VI B metal compound and theorganometallic compound may take place at temperatures which range frombelow ambient to elevated and pressures which would vary fromsubatmospheric to superatmospheric. The reaction should take place in asolvent, preferably an inert solvent; or in the reacting olefin itselfas a solvent; modifiers may be added to the catalyst mixture to alterthe type of reaction, reaction rate or selectivity of the reaction.Typical modifiers would include the various Lewis bases.

In more detail the instant invention pertains to a novel catalyst, meansfor preparing said catalyst and the use of such catalysts in thedisproportionation reaction.

To produce the catalyst of the instant invention, one must make use ofthe reaction product of a Group VI-B metal species of the type R[M(CO)X] with one or several organo metallic compound having the generalformula r LY In the above formulae R is a unipositive cation.

Generic examples of such cations include the followmg:

(1) Alkali metal ions such as Li, Na or K (2) Cations of the generaltype J Q+ where Q is a Group V element such as nitrogen phosphorous,arsenic and the like and I can be either hydrogen or an aromatic,saturated aliphatic or unsaturated hydrocarbon radical having up to 30carbon atoms. The four J radicals need not be identical but ispreferably tetraphenyl or a C to C alkyl group. Typical examples of suchcations are as follows:

tetrabutylammonium Cs+ tetraphenylphosphonium K+ tetraphenylarsonium Na+methyltriphenylphosphonium triphenylmethylammonium pyridiniumbenzyltrimethylphosphonium tetra(n-propyl)ammonium tetraphenylstiboniumtetradecylammonium M is a Group VI-B metal and would thus have to beselected from Cr, M0, or W, X may be any uninegratively charged ligandbut is preferably a halide such as chlorine or a pseudohalide. Examplesof such pseudohalides include cyanide, cyanate, thiocyanate, and azide.Other uninegatively charged ligands which may be utilized arecarboxylate groups such as acetate, trifluoroacetate, stearate, etc.

The organometallic derivative compounds would include organometallichalides, hydrides, alkoxides and the like. Consequently, L, the metallicelement, may be selected from Group I, Group II, or Group III metalsmore preferably the Group I-A, II-A, or III-A metals of atomic number 3to 31; the most desirable element for N is aluminum. Further, r may beany aromatic or aliphatic radical including halide, alkoxy and similarderivatives or hydrogen, Y is a halide or pseudohalide, n is an integerof from 1 to 3, m is an integer of from to 3 and their total is equal tothe valence of L. More specifically, r may be substituted orunsubstituted, saturated or unsaturated, but should preferably behydrocarbyl in nature and more preferably still would be a C to Chydrocarbyl. Thus, the general category of alkyl, aryl, alkaryl,aralkyl, cycloalkyl and cycloalkenyl would be included. Alkyl groupingsof C to C are especially satisfactory, as are aryl groupings of C to Calkaryl groupings of C to C and aralkyl groupings of C to C The cyclicgroupings, both cycloalkyl and cycloalkenyl are preferred when they have3 to carbons. The above groupings would include for example, methyl,ethyl, npropyl, isopropyl, isobutyl, secondary-butyl, tert-butyl, namyl,isoamyl, heptyl, n-octyl, n-dodecyl, and the like; Z-butenyl, and thelike, cyclopentyl-methyl, cyclohexylethyl, cyclohexylpropyl, and thelike; 2-phenyl ethyl, 2- phenyl propyl, 2-naphthyl ethyl, methylnaphthyl ethyl, and the like; cyclopentyl, cyclohexyl,2,2,1-bicycloheptyl, and the like; methyl cyclopentyl, dimethylcyclopentyl, ethyl cyclopentyl, methyl cyclohexyl, dimethyl cyclohexyl,S-cyclopentadienyl, and the like; phenyl cyclopentyl, and the like;phenyl, tolyl, xylyl, ethyl phenyl, naphthyl, cyclohexyl phenyl, and thelike. In general, the r group can contain up to about carbon atoms and Lmay be selected from such metals as lithium, magnesium, calcium,strontium, zinc, cadmium, boron, and aluminum.

Preferred organometallic compounds are aluminum derivatives of theformula R'AlY wherein R is selected from the group consisting ofhydrogen and C C hydrocarbyl radicals, including oxyhydrocarbyls, e.g.alkoxides, preferably alkyl radicals, wherein at least one R is ahydrocarbyl radical; and Y is a halide. More preferably alkylaluminumhalides are employed as the activating agent. Alkyl radicals of 1-12carbon atoms are most preferred. The preferred halides are Cl or Br withCl being the most preferred. Thus, compounds such as methylaluminumdichloride, ethylaluminum dichloride, methylaluminum sesquichloride,etc. may be employed. The most preferred compound, which appears to givethe best 4 catalyst is, however, methylaluminum dichloride. It isparticularly important that these organometallic compounds besubstantially and preferably completely, free of water since water cancause hydrolysis of the organometallic compounds, thereby inhibiting ordestroying its activating potential.

In some instances Lewis acids such as AlY wherein Y is a halide may beused in place of the organometallic derivative.

The two compounds, the Group VI-B metal and the organometallic arereacted at a temperature of about to C., preferably -50 to +100 C., andmost preferably 0 to 50 C. Pressure may vary between 0.1 and 1000 atm.,preferably 0.5 and 200 atm. and most preferably 1 and 100 atm. Thereactants are in the liquid phase. The ratio of organometallic compoundto Group VI-B metal compound may be varied between 05:1 and 50:1 on amole basis, preferably 1:1 to 15:1 on a mole basis and most preferably2:1 to 8:1. Contacting time for the reaction may vary between 1 min. andseveral days preferably 0.1 and 48 hours and most preferably 0.2 to 24hours.

The reaction proceeds most effectively within a solvent or the reactingolefin itself may act as a solvent; the solvent should be inert innature and is preferably organic. Typical solvents which may be utilizedare C to C alkanes, C to C aryls, C to C halo alkanes such as methylchloride, C to C haloaryls, and certain haloalkenes which have a halogensubstituted on the double bond. Examples of solvents which may be usedinclude pentane, hexane, decane, benzene, Xylene, carbon tetrachloride,dichloromethane, chlorobenzene, bromobenzene, tetrachloroethylene,trichloroethylene, etc.

Following the formation of the catalyst, suitable olefins may be addeddirectly in order to commence the disproportionation reaction. Thecatalyst may be generated in the presence of the reacting olefins.

The catalyst may also be deposited on an inert solid support such assilica or alumina.

The basic formula for the homo disproportionation of an olefin is asfollows:

In the above reaction R R R and R may be selected from the groupconsisting of C to C alkyl, aryl, alkenyl, alkaryl, aralkyl, cycloalkyl,cycloalkenyl or hydrogen. Additionally, halogenated derivatives of anyof the preceding compounds may also be utilized provided that thehalogen is more than two carbon atoms removed from the double bond; atleast one of the group consisting of R R and R and R is an aryl radicalor an R'CH radical wherein -R' is an alkyl, aryl, alkenyl, alkaryl,aralkyl, cycloalkyl or cycloalkenyl radical or a hydrogen atom.Halogenated derivatives of any of the aforesaid radicals may be utilizedproviding that the halogen is greater than 2 carbons removed from thedouble bond.

More particularly, R R R and R may be selected from the group consistingof C to C alkyl, C to C aryl aryl including those aryls in which twoaromatic rings are condensed, C to C alkenyl but not conjugated dienes,C7 to C20 alkaryls, C7 to C20 aralkyl, C3 to C20 cycloalkyl, C to Ccycloalkenyl radicals provided that there are no conjugated double bondswithin the cycle alkenyl radicals or a hydrogen atom. Again, halogenatedderivatives, preferably chlorine, of the previously mentioned radicalsmay be utilized providing the chlorine or halogen utilized is more thantwo carbons removed from the double bond.

As previously mentioned, at least one of the said R R R and R must be anaryl radical or an R'CH radical wherein R is a C to C alkyl, a C to Caryl, a C to C alkenyl, C to C alkaryl, a C to C aralkyl, a

5 C to C cycloalkyl or a C to C cycloalkenyl or a hydrogen atom. Themost preferred values for R R R and R are C to C alkyls, C to C arylsand C to C alkenyls and hydrogen provided that at least one of said 6The transformation of one or more cyclic monoor polyolefins in such amanner that a new cyclic polyene of higher molecular weight is produced.A general equation for such a reaction would be R R R and R is an arylradical or an R'CH radical 5 or an R is a C to C alkyl, C to C aryl, andC to C alkenyl and hydrogen. Additionally, the catalyst of the instantinvention is useful for cross disproportiona- CH OH=OH 6 tron; by crossdlsproportronatron 1t 1s meant those reac- (0112).. (H2).n :2 (CHM(CH2).n tions in which a mixture of two different olefins is reacted 1OH OH oH oH to form at least one olefimc product. At least one of theproducts obtained is different of either of the reactants. The generalconcept of cross disproportionation is illustrated y the followlngformula; In this case n and m are integers which may vary from R(R,)Q=C(Ra)R4 R(Ru)C=C(R1)Rg to and they may either be the same ordifferent. It R (R )C=C(R )R R(R2)C=C(RQ)RH is understood that in thisreaction the products may react RKR3 G=C R7 R8 R4(Ra)C=(Ra)Ri further ina similar manner to form materials of higher molecular weight.

Indicative of the homo disproportionation reaction and Thetransformation of one or more acyclic polyolefins the products producedis the following table. 20 so as to form cyclic monoor polyolefins andacyclic TABLE Products CHzCH=CH1 CH: CHaCH:=CHCH2C 2CHt CHz=CHCHzCH=CH2Qon=om In this case n is an integer varying from 2 to 30. The reverse ofthis reaction may also be carried out; thus one may employ an acyclicpolyefin as a starting material and can obtain a cyclic mono orpolyolefin and an acyclic mono or polyolefin of lesser molecular weightthan the starting material as products.

CHzCHz (CH3) C=C (CH3) CHzCHg monoor polyolefins. A general equation forsuch a reaction would be:

R2CH=CHR4 In this case n and m are integers and may vary from 1 to 20and may be either the same or different from each other.

In the above equations R through R; are selected from the groupconsisting of alkyl, aryl, alkenyl, alkaryl, aralkyl, cycloalkyl,cycloalkenyl, halogen derivatives of the aforesaid and hydrogen. It ispreferred that R through R be selected from the group consisting of Cthrough C alkyl, C to C aryl, C to C alkenyl, C-;C alkaryl, C to Caralkyl, C to C cycloalkyl and C to C cycloalkenyl, halogen derivativesthereof, preferably chlorine.

ceding reactions are as follows:

10:1 to 10,000:1 on a molar basis may be used with preferred ratios offrom 100:1 to 1000: 1.

TAB LE Reactants Products CHaCHzCH2CH=CHCHzCH2CH3 CH3CH=CHCH3CH3CH2GH=GH2 CHaCHzCHzCH CHCH CH=CH: CHaCH CHCH;

CHzCH=CH3 CH CH=CHCH1 CHZ=CH2 CHz=CHz ClIz==CHCHa Reaction conditions inthe above reactions are substantially identical to the reactionconditions utilized to form the Group VI-B organometallic catalyst ofthe instant invention. That is to say, the reactants are contacted attemperatures of 100 to +150 0, preferably 0 to 50 C. at pressures whichmay range from 0.1 and 1000 atm. and preferably 1 and 100 atm. Contacttimes will vary between 1 min. and several days, preferably between 0.2and 24 hours. The reactants should be contacted in the liquid phasewithin an inert solvent, preferably an organic inert solvent, or thereacting olefin itself may be employed as solvent. Typical solventswhich may be utilized are the C to C alkanes, C to C aryls, halogenatedC to C alkanes, C to C haloaryls and certain haloalkenes. Specificexamples of solvents include pentane, hexane, decane, benzene, xylene,carbon tetrachloride, methylene chloride, tetrachloroethylene,trichloroethylene, chlorobenzene. A wide range of ratios of reactants tocatalysts may be employed. Ratios of reactants to catalysts fromSPECIFIC EMBODIMENTS EXAMPLE 1.--Disproportionati0n of a linear terminalolefin with high olefin to catalyst ratio In a dried two ounce bottle0.00005 mole of (n-C H N[Mo(CO-) C1], was contacted with 10 ml.chlorobenzene and 10 m1. pentene-l at ambient conditions. To thismixture 0.4 ml. of 1.0 molar solution of methylaluminum dichloride inchlorobenzene was added in one portion and the reaction was allowed toproceed at atmospheric pressure at ambient temperature for 24 hours. Avolatile gas was bubbled otf during this time; at the end of 24 hoursthe mixture was stripped on a rotary evaporator under a 15 mm. vacuum.The products were collected by condensation in a trap cooled in a DryIce acetone 'bath and then analyzed by vapor phase chromatography. Theanalysis indicated that the product consisted of 46.4 mole percentpentene-l and 53.6 percent of octene-4 on a solvent free basis.

9 [EXAMPLE 2.Use of the Br derivative rather than Cl In this example anexperiment identical to Example 1 with regard to process conditions wascarried out except that the catalyst consisted of 0.0005 mole of and theactivator was 4 ml. of a 1.0 molar solution of ethyl aluminumdichloride; reaction time was again 24 hours. The products recovered, bythe technique defined in Example 1, consisted of 89.8 mole percentpentene-l, 0.7 percent pentene-Z and 9.5 percent octene-4 as determinedby vapor phase chromatography.

EXAMPLE 3.Use of Cr derivative rather than Mo In this example anexperiment identical to Example 1 was utilized except that the catalystconsisted of 0.0005 mole of (n-C H N[Cr(CO) Cl] and the activator was 2ml. of a 1.0 molar solution of methyl aluminum dichloride. The productrecovered and identified as in Example 1 by vapor phase chromatographywas 93.4 mole percent pentene-l, and 6.6 percent octene-4.

EXAMPLE 4.--Use of W derivatives In this example an experiment identicalto Example 1 was utilized except that the catalyst consisted of 0.0005mole of (n-C H N[W(CO) C1] and the activator was 4 ml. of a 1.0 molarsolution of methyl aluminum dichloride. The product after a period of 24hours was determined by vapor phase chromatography to be 30.8 molepercent pentene-l, 0.3 percent heptene, and 68.9 percent octene-4 on asolvent free basis.

EXAMPLE 5.Reaction carried out at elevated temperature A heavy-walledglass reaction vessel fitted with a Teflon valve capable of withstandingelevated pressures was charged with 0.0005 mole (n-'C H N[Mo( C) Br], 10ml. chlorobenzene and 10 ml. pentene-l. A quantity of 1.0 molar solutionof methylaluminum sesquichloride in chlorobenzene was added so that theeventual ratio of aluminum to molybdenum was 8:1. The valve was thenclosed and the reaction vessel was placed in an oil bath at 60 C. forfour hours. The vessel was then removed from the bath and allowed tocool to room temperature over a period of one hour. The valve was thenreopened to allow gaseous products to escape and the reaction mixturewas stripped on a rotary evaporator under vacuum. The products werecollected in a trap cooled to 78 C. over a period of 0.2 hour; theproducts were analyzed by vapor phase chromatography and on asolvent-free basis consisted of 86.2 mole percent pentene-l, 5.0 percentpentene-2, and 8.8 percent octene-4.

EXAMPLE 6.Addition of a Lewis base modifier A two ounce bottle wascharged with 0.0005 mole 0.0005 mole triphenylphosphine, 10 ml.chlorobenzene, and 10 n11. pentene-l. Four ml. of a 1.0 molar solutionof methylaluminum dichloride in chlorobenzene was then added. Thereaction was allowed to proceed at ambient temperature and atomsphericpressure; any gaseous products were allowed to escape. After 24 hoursthe reaction mixture was stripped on a rotary evaporator under a 20 mm.vacuum. The products were collected in a trap at --78 C. and atmosphericpressure. Analysis of the product by vapor phase chromatographyindicated that the products consisted of 78.3 mole percent pentene-l,14.9 percent pentene-2, and 6.8 percent octene-4 on a solvent freebasis.

EXAMPLE 7.-Disproportionation of a cyclic olefin A two ounce bottle wascharged with 0.0005 mole 10 ml. chlorobenzene and 10 ml. cyclopentene. Asufficient amount of a 1.0 molar solution of methylaluminumsesquichloride in chlorbenzene was added so that the aluminum molybdenumratio was 8:1. The reaction was allowed tov proceed for 24 hours atambient temperature and atmospheric pressure. The reaction mixture whichhad become very viscous was then stripped on a rotary evaporator,volatile products were collected in a trap at 78 C. Approximately 6.4grams of cyclopentene were recovered unchanged. Additionally, 1 gram ofa tough rubbery polymer remained in the flask after the volatilematerials had been removed.

EXAMPLE 8.Disproportionation of a long chain terminal olefin To a flaskcontaining 0.0005 mole (H'C4H9 4N [M0 10 g. eicosene-l, and 10 ml.chlorobenzene was added 4 ml. of a 1.0 molar solution of CH AlCl inchlorobenzene. The mixture was heated in an oil bath at 50 for 24 hours.The mixture was then poured into 300 ml. methanol and the white solidwhich precipitated was collected by filtration and dried. Analysis ofthe product by gas phase chromatography showed approximately 25 molepercent eicosene-l and 75 percent octatricontene-l9.

EXAMPLE 9.Disproportionation of an aryl substituted olefin To a flaskcontaining 0.0005 mole (ll-C4119) 4N [M0 10 ml. 4-phenylbutene-1 and 10ml. chlorobenzene was added 4 ml. of a 1.0 molar solution of CHgAlClz inchlorobenzene. The mixture was allowed to stand at room temperature for24 hours. The reaction was terminated by the addition of 5 ml. acetone.The resulting solution was analyzed by gas phase chromatography and wasfound to contain 35% 4-phenylbutene-1 and 65% 1,6-diphenylhexene-3 on asolvent free basis.

EXAMPLE 10.Disproportionation of an internal linear olefin To a twoounce bottle containing 0.0005 mole (ll-C4119) 4N [MO 10 ml. cispentene-Z and 10 ml. chlorobenzene was added 4 ml. of a 1.0 molarsolution of CH AlCl in chlorobenzene. The solution was allowed to standat room temperature for 24 hours. The mixture was then stripped on arotary evaporator under 20 mm. vacuum. Analysis of the products by gasphase chromatography showed a composition of 19.1 mole percent butene-2,48.8 percent pentene- 2, 31.3 percent hexene-3 and 0.8 percent hepteneson a solvent free basis.

EXAMPLE 1.Disproportionation of a branched olefin An experiment similarto that described in Example 10 was carried out except that 10 ml. 3methylbutene-l was used as the reacting olefin. The products comprisedof 80.7 mole percent 3-methy1butene-1 and 19.3 percent 2,5-dimethylhexene-3 on a solvent free basis as determined by gas phasechromatography.

EXAMPLE l2.-Disproportionation of a linear diolefin to form cyclicolefin product To a two ounce bottle containing 0.0005 mole 10 ml1,7-octadiene and 10 ml. chlorobenzene was added and 3 ml. of a 1.0molar solution of CHgAlClg in chlorobenzene. The reaction was allowed toproceed at room temperature and atmospheric pressure for 24 hours. Themixture was then stripped on a rotary evaporator under 20 mm. vacuum andthe products were analyzed by vapor phase chromatography. The productconsisted of greater than 99 percent cyclohexene on a solvent freebasis.

EXAMPLE 13 An experiment identical to that described in Example 12 wascarried outwith the exception that 10ml. 1,4-pentadiene was employed asthe reacting olefin. In this case the products as determined by vaporphase chromatography had the composition of 90.4 mole percent1,4-pentadiene, 0.2 percent 1,4-cyclohexadiene and 9.4 percent1,4,7-octatriene.

EXAMPLE 14.Cross disproportionation To a two ounce bottle containing0.0005 mole (n-C H N[Mo(CO) Cl], ml. chlorobenzene, 5 ml. trans-Z-buteneand 5 ml. trans-4-octene was added 4 ml. of a 1 molar solution of CHAlCl in chlorobenzene. The mixture was allowed to stand at roomtemperature and atmospheric pressure for 24 hours. The solution was thenstripped on a rotary evaporator under 20 mm. vacuum. The product wasanalyzed by vapor phase chromatography and was found to contain 33.3mole percent butene-2, 51.1 percent hexene-2, and 15.6 percent octene-4on a solvent free basis.

EXAMPLE An experiment identical to that described in Example 14 wascarried out except that a mixture of 5 ml. vinyl cyclohexane and 5 ml.trans-2-butene was used as the reacting olefin mixture. The compositionof the resulting product as determined by vapor phase chromatography wasapproximately 30 mole percent butene-2, 25 percent vinylcyclohexane and44 percent l-cyclohexylpropene on a solvent free basis.

EXAMPLE l6.Reaction run without solvent To a two ounce bottle containing0.0010 mole (n-C H N[Mo(CO) Cl] and ml. pentene-l was added 0.82 gram ofliquid methylaluminum sesquichloride. The reaction was allowed toproceed at room temperature and atmospheric pressure for 3 hours. Themixture was then stripped on a rotary evaporator and the product wasanalyzed by gas phase chromatography. The composition of the product was18.4 mole percent pentene-l, 0.2 percent hexene, 0.4 percent heptenesand 81.1 percent octene-4.

EXAMPLE 17.-Disproportionation of cyclic olefin to form polymer To abottle containing 0.0020 mole (n-C H N [Mo (00) C1] 40 ml. chlorobenzeneand 40 ml. cyclooctene was added 8.0 ml. of a 1.0 molar solution ofCHgAlClz in chlorobenzene. The mixture was stirred for 15 minutes thenthe resulting viscous solution was poured into 1000 ml. methanol. Awhite rubbery polymer precipitated which was collected on a filter,washed with an additional 500 ml. methanol and finally dried under highvacuum. The yield of dried polymer was 31.0 grams.

EXAMPLE 18.Cross disproportionation of cyclic and linear olefin to formlinear diolefin A mixture of 0.002 mole (n-C H N[Mo(CO) Cl], 40 ml.chlorobenzene and 40 ml. cyclohexene was placed in a stainless steelautoclave then 16 ml. of a 1.0 molar solution of CH AlCl was added underargon pressure. Ethylene gas was then introduced until the totalpressure of ethylene was 800 p.s.i. The mixture was vigorously stirredunder this pressure for 16 hours. The gas pressure was then released andthe reaction mixture was stripped on a rotary evaporator under vacuum.The product was analyzed by vapor phase chromatography and was found tobe 98.6 mole percent cyclohexene and 1.4 percent 1,7- octadiene on asolvent free basis.

What is claimed is:

1. A process for preparing a catalyst which consists essentially ofcontacting a metallic composition having the formula R[M(CO) X] whereinR is selected from the group consisting of alkali metal ions and cationsof the type J Q wherein Q is selected from the group consisting ofnitrogen, phosphorus and arsenic, and J is selected from the groupconsisting of hydrogen and C -C hydrocarbyl radicals, M is a Group VI-Bmetal and X is a uninegatively charged ligand, selected from the groupconsisting of halide, cyanide, cyanate, thiocyanate, azide, acetate,trifiuoroacetate and stearate, with an activator, said activatorconsisting essentially of com pounds of the general formula AlY whereinY is a halide, at a temperature of about 100 to +150 C., and a pressurebetween 0.1 to 1000 atmospheres, whereby a catalyst is formed.

2. A process for preparing a catalyst which consists essentially ofcontacting a metallic composition having the formula R[M(CO) X] whereinR is selected from the group consisting of alkali metal ions and cationsof the type J Q wherein Q is selected from the group consisting ofnitrogen, phosphorous and arsenic, and J is selected from the groupconsisting of hydrogen and C C hydrocarbyl radicals, M is a Group VI-Bmetal and X is a uninegatively charged ligand, selected from the groupconsisting of halide, cyanide, cyanate, thiocyanate, azide, acetate,trifluoroacetate and stearate, with an activator, said activatorconsisting essentially of an organometallic compound, saidorganometallic compound selected from the group consisting of compoundshaving the general formula r LY wherein r is independently selected fromthe group consisting of C to C hydrocarbyl radicals, L is selected fromthe group consisting of Group I-A, II-A and III-A metals, said metalshaving an atomic number of from 3 to 31, Y is a halide, n is an integerof from 1 to 3, and m is an integer of from 0 to 3, n and m having atotal equal to the valence of L, at a temperature of from about 100 to+150 C. and a pressure of between 0.1 and 1000 atmospheres, the molarratio of organometallic compound to metallic composition varying between0.5 :1 and :1, whereby a catalyst is formed.

3. The process of claim 2 wherein J is selected from the groupconsisting of phenyl and C to C alkyl radicals.

4. The process of claim 3 wherein the process takes place in an inertsolvent.

5. The process of claim 3 wherein said uninegatively charged ligand is ahalide.

6. The process of claim 3 wherein said halides are chlorides.

7. The process of claim 3 wherein the various Js are independentlyselected from the group consisting of C to C alkyl groups.

8. The process of claim 3 wherein r is selected from the groupconsisting of C to C alkyl radicals.

9. The process of claim 4 wherein said solvent is a C to C alkane.

10. The process of claim 4 wherein said solvent is halogenated.

11. The process of claim 3 wherein said contacting takes place at atemperature of 0 to 50 C., a pressure of 1 to atmospheres for a periodof 0.2 to 24 hours.

12. The process of claim 3 wherein the molar ratio of organometalliccompound to metallic composition varies from 2:1 to 8:1.

. The process of claim 3 wherein M is Mo. The process of claim 3 whereinM is Cr.

. The process of claim 3 wherein M is W.

. The process of claim 3 wherein L is Al.

17. The process of claim 3 wherein said organometallic compound ismethylaluminum dichloride.

18. The product of claim 4.

(References on following page) 13 14 References Cited FOREIGN PATENTSUNITED STATES PATENTS 1,159,053 7/1969 Great Britain 252443 9/1970Singleton 252-429 R Lyons et a1. A X 5 P. Pl'lmary Examlnel 8/1960Coover et a1. 252-431 N X Us Cl XR 3/1963 Coover et a1. 252-429 B X 9 9B k 2 0-5 3 X 252-428, 431 R, 431 C, 431 N, 431 P, 438, 441; 5/1970Hughes 252431 C X D

